Stilbene compounds

ABSTRACT

New stilbene compounds of the formula   WHEREIN R1 represents alkyl with 1 to 4 carbon atoms R2 and R3 independently of one another represents hydrogen or methyl and M represents hydrogen, an alkali metal or an optionally substituted ammonium cation. These compounds are useful as optical brighteners.

United States Patent Fringeli STILBENE COMPOUNDS [75] Inventor: Werner Fringeli, Basel, Switzerland [73] Assignee: Ciba-Geigy AG, Basel, Switzerland [22] Filed: Dec. 18, 1972 [21] Appl. No.: 316,154

[30] Foreign Application Priority Data Dec. 27, 1971 Switzerland 18965/71 R -N H [52] US. Cl..... 260/240.l; l17/33.5 R; 117/335 T; 252/3012 W; 252/543; 260/240 B [51] Int. Cl C09b 23/00 [58 Field of Search 260/240 B, 240.1

[56] References Cited UNITED STATES PATENTS 2,945,762 7/1960 Carroll et al. 260/240 B 3,177,207 4/1965 Siege] et a1. 260/240 B 3,392,122 7/1966 Obayashi et a1 260/240 B X Fleck 260/240.1 X

[4 1 July 15,1975

FOREIGN PATENTS OR APPLICATIONS 870,263 3/1953 Germany 260/240 B Primary Examiner-John D. Randolph Attorney, Agent, or Firm-Joseph G. Kolodny; Edward McC. Roberts; Prabodh I. Almaula [57] ABSTRACT New stilbene compounds of the formula M represents hydrogen, an alkali metal or an optionally substituted ammonium cation.

These compounds are useful as optical brighteners.

4 Claims, N0 Drawings 1 STILBENE COMPOUNDS The present invention relates to new derivatives of 4,4'-bis-triazinylamino-stilbene-2,2'-disulphonic acid,

symmetrically and asymmetrically substituted deriva- 20 tives of 4,4'-bis-triazinylamino-stilbene-2,2'- disulphonic acid which can be used as optical brighteners are already known in large numbers, for example from German Pat. Specification Nos. 870,263 and 1,183,882.

As compared to structurally comparable previously known 4,4"bis-triazinylamino-stilbene-Z,2'- disulphonic acids, the compounds according to the invention defined below are above all distinguished by very good absorption, especially on cotton, over the entire temperature range over which the washing agents are employed.

The compounds according to the invention are asymor methyl and M denotes a hydrogen, alkali metal or optionally substituted ammonium cation. With the scope of the formula (1), the compounds of the formula (2) SO M wherein R denotes alkyl with l to 4 carbon atoms and M denotes a hydrogen, alkali metal or optionally substituted ammonium cation, should be singled out.

The preferred compound is 4-(2-anilino-4- morpholino-l ,3,5-triazinyl-( 6 )-amino )-4'-( 2-anilino-4- ethylamino-l ,3,5-triazinyl-( 6 )-amino)-stilbene-2,2 disulphonic acid in the form of the sodium salt. Further, 4-( 2-anilino-4-morpholinol .3,5-triazinyl-( 6 amino)-4-( 2-anilino-4-isopropylamino-l ,3.5-triazinyl- (6)amino)-stilbene-2,2'-disulphonic acid and its sodium salt are also of particular interest. The compounds of the formula (1) can be manufactured analogously to known processes.

Advantageously, 4-nitro-4'-amino-stilbene-2,2'- disulphonic acid or a salt thereof is condensed in a known manner with cyanu'ric chloride to give 4-nitro- 4-(2,4-dichloro-l ,3,5-triazinyl-( 6 )-amino )-stilbene- 2,2'disulphonic acid, whereupon the latter is reacted,

metrical substitution products of 4,4-bistriaZinylamino-stilbene-2,2'-disulphonic acid and cor- 35 in each case in optional sequence, with la) aniline and respond to the formula (lb) optionally methyl-substituted morpholine or 2a) 2/ 'i *i R N CH =CH N N 2 N H N-- R NH SO M N o wherein R denotes alkyl with 1 to 4 carbon atoms, R and R independently of one another denote hydrogen aniline and 2b) an alkylamine with l to 4 carbon atoms. to give a compound of the formula NH NT (4 N/ RI-NH wherein R R R and M have the abovementioned meaning.

Thereafter, the nitro group of a condensation product thus obtained is converted by reduction, for example with iron in the presence of an acid, into the amino group and the latter is again converted into a derivative, in an analogous manner to that described above for the other amino group, so as to produce a compound of the formula (1). For this purpose, the amino compound resulting from the nitro compound of the formula (3) is reacted in optional sequence with aniline and an alkylamine with 1 to 4 carbon atoms, or the compound manufactured from the nitro compound of the formula (4) is reacted in optional sequence withaniline and with optionally methylsubstituted morpholine.

The manufacture of compounds of the formula l is furthermore also possible, for example, starting from 4,4-diamino-stilbene-2,2'-disulphonic acid or its salts, by reacting the latter firstly with 2 mols of cyanuric chloride, after which the condensation product obtained is reacted with 2 mols of aniline and the resulting reaction product is condensed, in a third stage, with an excess of a mixture of optionally methyl-substituted morpholine and alkylamine with l to 4 carbon atoms, the composition of the mixture being in accordance with the reaction velocities of the individual components.

The new stilbene compounds of the formula (1) are appropriately isolated from the reaction mixture as metal salts. They are suitable for use as optical brighteners for washing agents. Suitable washing agents for example contain, as detergent substances, anionic compounds such as alkali metal salts, especially sodium salts, of higher fatty acids, alkylarylsulphonates, above all dodecylbenzenesulphonate or tetrapropylbenzenesulphonate, secondary alkyl sulphates with a higher secondary alkyl radical, fatty alcohol sulphates, such as dodecyl sulphate, or sulphated addition products of 2 to 3 mols of ethylene oxide to dodecyl alcohol, or nonionic compounds, such as fatty alcohol polyglycol ethers or higher alkylphenol polyglycol ethers. In addition, these washing agents can contain fillers and auxiliaries which are customary in the textile finishing industry, for example alkali metal polyphosphate and polymetaphosphate, alkali metal pyrophosphate, alkali metal silicates, alkali metal carbonates, alkali metal borates, alkali metal perborates, alkali metal salts of carboxymethylcellulose, foam stabilisers, such as hydroxyalkylamides of higher fatty acids or complexones, such as soluble salts of ethylenediaminetetraacetic acid. Furthermore the washing agents can contain for example, antistatic agents, skin protection agents o N cH=cH i 2 I N $03M 7 Q-cIficHQNO SO M 3 which are non-greasy, such as lanolin, enzymes, antimicrobial agents, perfumes and other optical brighteners.

The content of brighteners of the formula l) or (2),

according to the invention, in the liquid or pulverulent final washing agent can be 0.001 to 2% by weight, preferably 0.005 to 0.5% (relative to the washing agent).

The new stilbene compounds of the formula (1) are absorbed from aqueous solution, especially from aqueous solution containing washing agents of the abovementioned type, onto cellulose material, such as cotton, and on polyamides, over the entire temperature range which may be used for washing (for example 2592C). The content of whiteners of the formula l in aqueous textile treatment solutions is advantageously 0.001 to 0.2% (relative to the weight of the material to be brightened). The material treated with liquors containing brighteners of the formula (1) acquires a pure white appearance with a blue-violet shade. The whiteners according to the invention impart to the textile material, when it is repeatedly washed, a good increase in the degree of whiteness without undesired discolouration.

In the examples which follow the parts are always parts by weight and the percentages are always percentages by weight.

EXAMPLE 1 A solution of 18.4 parts of cyanuric chloride in 100 parts of acetone is poured into 200 parts of a mixture consisting of equal parts of ice and water and a solution, neutralised with sodium hydroxide, of 40 parts of 4-nitro-4'-amino-stilbene-2,2'-disulphonic acid in 400 parts of water is added dropwise over the course of one hour to the resulting suspension at 05C whilst stirring and simultaneously keeping the pH value of the reaction mixture at between 6 and 7 by adding a 15% strength sodium carbonate solution. The mixture is stirred for a further half hour and 9.3 parts of aniline are then added, the temperature is raised to 35C over the course of about half an hour and the mixture is stirred for a further hour at this temperature. At the same time, the resulting hydrochloric acid is neutralised by gradual addition of a 15% strength sodium carbonate solution (pH value between 7 and 8). Thereafter, 10 parts of morpholine are added to the reaction mixture, the temperature is raised to C and the mixture is stirred for about three hours at this temperature whilst simultaneously maintaining a pH value of between 9 and 10 by dropwise addition of a 15% strength sodium hydroxide solution. The condensation product of the formula salt of the 4-amino-4'-(2-anilino-4-morpholino-l,3,5-

which has separated out after cooling to room temperaat this temperature. The resultinghydrochloric acid is ture is filtered off and washed with a sodium chloride neutralised by gradual addition of a 15% strength so-' solution. The product dissolvedin 400 parts Of water is dium arbonate solution (pH value between '7 and 8) now de dr pwi e r he co rse f 1 h r at 11.3 parts of 50% strength aqueous monoethylamine 90-lO0C, to a reducing solution consisting of 200 5 solution are now added to the reaction mixture, the parts of water, 30 parts of iron filings and 3 parts of glatemperature is raised to 80C and the mixture is stirred cial acetic acid. As soon as the nitro compound can no for three hours at this temperature whilst at the same longer be detected, the solution is rendered alkaline time maintaining a pH value of between 9 and 10 by with sodium carbonate and filtered and the disodium adding a strength sodium hydroxide solution.

0 The mixture is now allowed to cool slowly to room triazinyl-(6)-amino)-stilbene-2,2-disulphonic acid temperature and the condensation product which has produced is separated out from the filtrate by adding precipitated is filtered off, washed with sodium chlosodium chloride,filtered off, washed with sodium chloride solution and dried. The disodium salt of 4-(2- ride solution and dried. 1 anilino-4,-morpholino-l,3,5-triazinyl-(6)-amin0)-4-(2- 67 parts of the product obtained in this manner are 15 anilino-4-ethylamino-l,3,5triazinyl-(6)-amino)- dissolved in 800 parts of water and the resulting solustilbene-2,2'-disulphonic acid thus obtained, of the fortion is added dropwise over the course of l hour at mula I V o o H /"-N N N N CH=CH N \N IN I SONaH NH-CH 0-5C to a suspension which has been obtained by is a pale yellowish, water-soluble powder which can be mixing 18.4 parts of cyanuric chloride, dissolved in lOO used as a brightener in washing powders.

parts of acetone, with 100 parts of ice and 100 parts of water. In order to neutralise the hydrochloric acid pro- EXAMPLE 2 duced,the pH value of the reaction mixture is at the If, instead of 11.3 parts of 50% strength aqueous same time kept at between 6 and 7 by dropwise addimonoethylamine solution, 8 parts of strength tion of a 15% strength sodium carbonate solution. aqueous monomethylamine solution, 7.5 parts of n- Thereafter, the reaction mixture isstirred for half an propylamine, 7 5 parts of iso-propylamine or 9.5 parts hour. 9.3 parts of aniline are then added, the temperaof n-butylamine are employed and in other respects the ture is raised to 35C over the course of about half an procedure described in Example 1 is followed, the hour and the mixture is stirred for a further two hours 0 compounds of the formulae NH-CH @NH SOSNu NH H-CH CH CH I $03 No Q NH 9) a v N or' c 1 H C H N H N 50 m: l f z z z a v I 1 V 25 I are obtained as pale yellowish, water-soluble powders. EXAMPLE 4 If, instead of .10 parts of morpholine, 13.2 parts of EXAMPLE 3 2,6-dimethylmorpholine are employed, and instead of 30 11.3 parts of 50% strength aqueous ethylamine solulnstead of 10 'fi of morpholme, parts of tion, 8 parts of 50% strength aqueous methylamine so- 2,6d1methylmorpholme are employed,and1n other remien 8 parts of mPrOPYlamine .8 I parts Qf. spects the procedure described v1n Example 1 1s folpropylamine or lopans ofmbutylamine are employ-w 10wedthe compound of the formula and in other respects the procedure described in Exam- Q I"v lil- 1) CH 0 N NM H=CHY N 3 Nil-C 11 is obtained as a pale yellowish, water-soluble powder. ple 1 is followed, the compounds of the formulae Nil-C11 0 N S0 Na c11 NH-CH CH CH SON 2 2 3 V a 3 g or O N NH-CH cl-i CH Q Q H i I N CH3 N y CH=CH N( N I NH-CH CH CH CH o N i so No 2 2 2 3 3 CH 3 are obtained as pale yellowish, water-soluble powders. i i h case dissolved in 2.5 ml of 1 N sodium hydroxide solution and 100 ml ofwater and converted EXAMPLE 5 into a homogeneous paste with 100 g of a heavy duty A mixture of 356 parts of a 50.7% strength ethylamwashing agent consisting of 15.7 parts of sodium ine solution and 36 parts f m rp li in 0 p rts f dodecylbenzenesulphonate, 3.7 parts of fatty alcohol acetone is added at 40C, whilst stirring, to a sussulphonate, 2.7 parts of coconutacid monoe th anolpension of 3672 Parts Of the diSOdium alt of 4,4bis- 35 amide, 39.0 parts of sodium tripolyphosphate, 4.0 parts (2-anilino-4-chloro-l,3,5-triazinyl-(6)-amin0)- of sodium silicate, 2.0 parts of magnesium silicate 1.0 Stilbene-2,2-disulphonic acid (manufactured by conpart of carboxymethylcellulose, 0.5 part of the tetrasodensation of 2 mols of cyanuric chloride with 1 mol of dium salt of ethylenediaminetetraacetic acid, 24.7 4,4'-diaminostilbene-2,2'-disulphonic acid and 2 mols parts of sodium sulphate and 6.7 parts of water; thereof aniline) in 3,000 parts of softened water. Thereafter 4( after the paste is sprayed in a spray drier. Washing the temperature of the reaction mixture is raised to agents of a high degree of whiteness are obtained. 90C over the course of two hours whilst atthe Bleached cotton fabrics are washed for 15 minutes at same time keeping the pH value of the reaction mix- 25 to 92C in a washing liquor which in each case conture, which now slowly dissolves, at 10.5 by addition of tains 4 g/litre of a washing agent, containing brightener, a 15% strength sodium hydroxide solution, and the 45 described above, using a liquor ratio of 1:20, and are mixture is stirred for three hours at C whilst mainrinsed and dried. Very attractively brightened fabrics taining a pH value of 10.5. Thereafter the excess ethylare obtained.

amine is distilled off and the reaction mixture is slowly What we claim is:

cooled to room temperature. The product of the for l. Stilbene derivatives of the formula I S0 H I mula (6) which has separated out is filtered off, washed wherein 1 denotes alkyl with 1 t0 4 Carbon atoms, 2 with sodium chloride solution and dried. 360 parts of and R independently of one another denote hydrogen a yellow, water-soluble powder are obtai d. 5 or methyl and M denotes a hydrogen, alkali metal or optionally substituted ammonium cation. EXAMPLE 6 2. Stilbene derivatives according to claim 1, corre- 0.1 to 0.2 g of a brightener of the formulae (6) to pending to the formula c H =c H N N H I N O l wherein R, denotes alkyl with l to 4 carbon atoms and 4. The stilbene derivative according to claim 1, cor- M denotes a hydrogen, alkali metal or optionally substiresponding to the for l tuted ammonium cation. H 15 3. The stilbene derivative according to claim 1, cor- 30 responding to the formula Nlli H Q N F l H CH CH N 

1. STILBENE DERIVATIVES OF THE FORMULA
 2. Stilbene derivatives according to claim 1, corresponding to the formula
 3. The stilbene derivative according to claim 1, corresponding to the formula
 4. The stilbene derivative according to claim 1, corresponding to the formula 